Novel diperchloryldiphenoquinones and process for their manufacture



in several applications.

United States Patent 3,112,327 NOVEL DIPERCI-ILORYLDIPHENOQUINONES AND PROCESS FOR THEIR MANUFACTURE David M. Gardner, North Wales, and Robert E. Oesterling, Flourtown, Pa., assignors to Pennsalt Chemicals Corporation, Philadelphia, Pa., a corporation of Pennsylvania Filed Jan. 4, 1961, Ser. No. 80,694

No Drawing.

4 Claims. (Cl. 260-396) This invention relates to novel chemical compounds and to a process for their manufacture. More particularly, this invention deals with diquinoids which we call diperchloryldiphenoquinones and which have the structure:

ClOa

It is known to oxidize aniline 'with sodium dichromate and sulfuric acid to obtain benzoquinone in accord with the following reaction mechanism:

aniline (cg. NHz

does not undergo an analogous reaction, but proceeds in a manner to yield a diperchloryldiphenoquinone characterized by the above structure. These novel compositions have several unusual properties which make them useful Although the compounds melt sharply when heated slowly, they are thermally sensitive and explode upon rapid heating. The compounds are also shock sensitive and are thus useful explosives of value in blasting caps or as a primary explosive and may be compounded in accord with the methods used for high explosives (erg, hexanitrodiphenylamine, 2,4,6-trinitrophenylmethylnitramine, etc.) as described on pages 1 to 91 of vol. 6 of the Kirk-Othmer Encyclopedia of Chemical Technology.

The compounds also have fungicidal and bactericidal properties due to their quinoid structure. Sun-prising also is their stability to reduction, no dihydroxy biphenyl derivative being obtained upon treatment with sulfurous acid which readily converts unsubstituted diphenoquinone to 4,4-dihydroxy biphenyl.

It will be understood from the above structures that the particular isomeric diperchloryldiphenoquinone will de- 2 pend upon the starting .perchloryla-niline. 'That is 3-perchlorylaniline will yield 2,6'-diperchloryldiphenoquinone 0103 whereas Z-perchlorylaniline will yield 3,5'-diperchloryldiphenoquinone. The 2,2 structure is unlikely due to hindrance of the large C10 groups which prohibit the coplanarity of the two rings which is required for formation of the d-iphenoquinone system.

As indicated, the diperchloryldiphenoquinone is prepared by the oxidation of the perchlorylaniline with solutions of sodium dichromate and sulfuric acid. The process is carried out at temperature of between about -10 C. and about 50 C., the upper temperature being limited by the degradation of organic compounds that occurs with solutions of 'chromic and sulfuric acids. The product is recovered from the reaction mass readily by filtering oil the insoluble crude product and purifying it in accord with the common techniques of organic synthesis, e.g. crystallization from solution.

The following examples will serve to further describe the invention:

Example 1 (All parts are by weight.)

A solution of 1.1 parts of 3-perchlorylaniline hydrochloride (prepared by the method described by Inman, Oesterling and Tyczkowski in J.A.C.S. 5286, 1958) in 40 parts of dilute sulfuric acid was cooled to 0 C. A solution of 2.5 parts of sodium dichromate in 15 parts of water was then dropped into the B-perchlorylaniline hydrochloride solution with eflicieut stirring to mix the reaction products. Stirring was continued for 5 hours while holding the temperature at 0 to 10 C. and the reaction mass was then filtered to obtain 0.7 parts of a brown solid. This solid product was dissolved in 16 parts of chloroform with gentle Warming (50 to 60 C.) to obtain a bright red-orange solution and a small amount of insoluble material which was filtered oif. Light petroleum ether was added to the chloroform solution until precipitation of a product was obtained and the mass cooled to 0 C. The solid was filtered oif to obtain 0.45 parts of crude product. The orange product was recrystallized from carbon tetrachloride to obtain 2,6-diperchloryldiphenoquinone as orange granules, M.P. to 182 C. Analysis indicated the following: Calcd/ foundpercent C 41.28/41.41; percent H 1.73/ 1.84; percent Cl 2031/2049; mol. wt. 349/359.

The infrared spectrum confirmed the structure in indicating the presence of quinoid carbonyl (5.9 ,u. band) and the perchloryl group (8.4 ,u band).

The diperchloryldiphenoquinone was recovered unchanged when its solution in aqueous ethanol was treated with sulfur dioxide.

Example 2 A 50 mg. sample of pure crystalline 2,6'-diperchloryldiphenoquinone was placed in a brass cup on a Drop- Weight Impact Testing Apparatus and subjected to 20 kilogram centimeters impact. The sample detonated sharply, emitting a bright flame and shattering the brass cup.

3 4 It will be understood that numerous changes may he 2. 2,6'-diperchloryldiphenoquinone. made from the above specific description of the inVen- 3. Aprocess for preparing diperchloryldiphenoquinones tion Without departing from its spirit and scope. which comprises oxidizing a perchlorylaniline at a tem- We claim: perature between about 10 and about 50 C. with a 1. A idiperchloryldiphenoquinone of the formula 5 mixture of sodium dichromate and sulfuric acid.

4. 3,5-diperchloryldiphenoquinone.

O: :0 No references cited.

wherein the quinoid rings are coplaner. 

1. A DIPERCHLORYLDIPHENOQUINONE OF THE FORMULA 